CN103663478B - A kind of preparation method of dendroid pore passage structure mesoporous spherical nano Sio 2 particle - Google Patents
A kind of preparation method of dendroid pore passage structure mesoporous spherical nano Sio 2 particle Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of mesoporous spherical nano Sio 2 particle of dendroid pore passage structure, the template that the method is used for cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt, alkali source for organic molecule amine, silicon source be tetraalkyl esters of silicon acis, the cosurfactant adding is three block neutral polymer F127; The silicon source that mole consists of of raw material: template: organic molecule amine: F127: water=1:0.03～0.06:0.001～8.0:0.0001～0.1:20～1000, the particle diameter of particle can be realized Effective Regulation within the scope of 20～200nm. The amount that simple regulation and control cosurfactant F127 adds with and the order that adds before and after silicon source, can effectively regulate the particle size of the mesoporous silicon oxide of dendroid pore passage structure. Synthetic method of the present invention is simple, the cycle is short, cost is low, reproducible, be a kind of eco-friendly synthetic method.
Description
Technical field
The present invention relates to a kind of preparation method of mesopore molecular sieve, specifically have a kind of high stability single dispersionThe preparation method of the mesoporous spherical nano Sio 2 particle of dendroid pore passage structure.
Background technology
Dendrimer and polymer (Denderimer) material is at targeted drug delivery, organizational project, gene deliveryThe medical domains such as treatment, molecular image, non-invasive procedures synergy treatment have broad application prospects, great for such as cancer etc.The early diagnosis of disease has great importance with efficient treatment. But due to the intrinsic heat of organic material carrier self, chemistryThe defect of poor stability, causes coated medicine easily in human body, to produce the explosion type of medicine because of the decomposition of organic carrierDischarge, and there is medicine covering amount shortcoming on the low side in organic carrier. There is the inorganic nano pharmaceutical carrier of nano pore structureThere is high medicine useful load, be easy to the inside and outside duct of modification, good heat and chemical stability, early stage in major diseaseDiagnosis and targeted drug have demonstrated unique advantage (Journal of Inorganic Materials, 2013,28,1-11.) on carrying. DendroidMesoporous silica nano-particle is with design feature and physical mechanical strength and the larger ratio of organic dendrimerSurface area and pore volume have caused studies interest (Adv.Mater.2013, DOI:10.1002/ widelyadma.201302189）。
The synthetic work of dendroid mesoporous nano-grain has been obtained some progress, how to make full use of that these are multi-functionalNano material, replace or improve existing some have the nano material of open defect or drawback, also need more effort, especiallyThat the accuracy controlling (20～200nm) of particle size and the research that forms mechanism are also quite short of. Japanese scientist in 2009Okuyama seminar, utilizes lysine (Lysine) to report the earliest large aperture branch as alkali source and germination inhibitorSynthetic (MicroporousMesoporousMater.2009,120,447 of shape mesoporous silica spheres shape particle453.), but need to be by means of complicated microemulsion system, synthetic method complexity, and synthetic cost is higher. Subsequently, BassetThe Jiao Zheng seminar of (Angew.Chem.Int.Ed.2010,49,9,652 9656.) and domestic Shanghai University(Chem.Commun.2010,46,6783-6785.) carried out this synthesis strategy further perfect, but still usesMicroemulsion system, and particle size is confined to 200 nanometer left and right. Chinese patent CN102616795A and research paper (J.Am.Chem.Soc., 2013,135,2,427 2430.) reported use cetyl trimethyl p-methyl benzenesulfonic acid ammoniumSalt (CTATos), as template, can synthesize highly monodispersed dendroid mesoporous silica nano-particle, only need pass throughDirectly the way of suction filtration just can obtain end product, has realized first the feather weight of dendroid mesoporous silica nano-particleSynthetic, and synthesis mechanism has been carried out to further investigation. Although this synthetic method preparation is simple, the particle obtaining againAfter ultrasonic dispersion,, easily there is serious reunion and coagulation in colloidal stability extreme difference after a few minutes; In addition, find by simpleChange experiment parameter, as the kind of reaction temperature, reaction time and solvent and amount, be difficult to realize the precision regulating of particle sizeControl. Therefore research and develop that new synthetic technology realizes the accurate modulation of particle size and the stable dendroid mesoporous silicon oxide of colloidal state is receivedThe quantification of rice grain is produced has important theory and realistic meaning.
Summary of the invention
The object of the present invention is to provide a kind of particle size accuracy controlling (20～200nm) and the stable tree of colloidal stateThe quantification synthetic method of dendritic mesoporous silica nano-particle.
The object of the present invention is achieved like this:
A preparation method for dendroid mesoporous silica nano-particle, the method comprises following concrete steps:
A, by deionized water, organic molecule amine, cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt (CTATos) sun fromSubtemplate agent and cosurfactant F127 join in reaction vessel successively, and 80 DEG C of constant temperature are stirred to solution and clarify surperficiallyActivator solution;
B, silicon source is joined rapidly in step a solution, 80 DEG C of constant temperature stir 2 hours, be cooled to transfer to after room temperature anti-Answer in still crystallization or directly product is carried out to centrifugation, washing dry, obtain end product;
Wherein:
The mol ratio of described material is silicon source: template CTATos: organic molecule amine: F127: deionized water=1:0.03～0.06:0.001～8.0:0.0001～0.1:20～1000；
Described template is cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt, is called for short CTATos; CosurfactantF127 is the large molecule of a kind of three block neutral polymer, is abbreviated as F127; Silicon source is tetraalkyl esters of silicon acis, as tetramethoxy silicic acidEster or tetraethoxy esters of silicon acis;
Described organic molecule amine is tri methylol amino methane, ethamine, propylamine, butylamine, triethylamine, tripropyl amine (TPA), three secondHydramine, monoethanolamine or diethanol amine;
The principal character of this synthetic method is the amount that adds by regulation and control cosurfactant F127 and before silicon sourceAfter the order that adds, the particle diameter that can realize the mesoporous silica particles with dendroid pore passage structure 20～200nm itBetween accurately regulation and control. If F127 added before adding silicon source, can obtain the dendroid mesoporous two that particle size is less than 60nmMonox nanometer particle; If added, obtain the dendroid meso-porous titanium dioxide that particle size is greater than 100nm after silicon sourceNano silicon particles.
Cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt used in the present invention (CTATos) cationic surfactantCome from German Merck chemical reagents corporation; Other reagent is domestic commercially available.
The present invention is compared with existing preparation method, and tool has the following advantages:
(1), the accurately regulation and control between 20～200nm of dendroid mesoporous silica nano-particle particle diameter have been realized.
(2), simple, the synthetic cost of preparation method is low.
, sample just can be distributed in the middle of ethanol polar protic solvent by the method for simple ultrasonic processing, obtainHigh stability colloidal solution.
Brief description of the drawings
Fig. 1 is the scanning electricity that the present invention added dendroid mesoporous silica nano-particle prepared by F127 before silicon sourceMirror (SEM) figure, particle size 50nm;
Fig. 2 is the high-resolution that the present invention added dendroid mesoporous silica nano-particle prepared by F127 before silicon sourceTransmission electron microscope (TEM) figure;
Fig. 3 is the scanning electricity that the present invention adds dendroid mesoporous silica nano-particle prepared by F127 after silicon sourceMirror (SEM) figure, particle size 120nm;
Fig. 4 is the high-resolution that the present invention adds dendroid mesoporous silica nano-particle prepared by F127 after silicon sourceTransmission electron microscope (TEM) figure.
Detailed description of the invention
Below by embodiment, the invention will be further described, and its object is only better to understand research of the present inventionContent but not limit the scope of the invention.
Embodiment 1
First 2.74g cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt (CTATos) and 8.33gF127 are joined and containedThere is the triethanolamine (TEAH of 144ml deionized water, 14.92g3) beaker in, 80 DEG C of constant temperature stir and become clear to solution in 1 hourClearly, then 20.83g tetraethoxy esters of silicon acis (TEOS) is joined rapidly in this beaker, 80 DEG C of 2 of constant temperature continuation stirrings are littleTime, obtain stable colloidal suspension liquid, this mixture mole consist of SiO2:CTATos:TEAH3:F127:H2O=1:0.06:1:0.0095:80; By centrifugal the mixture obtaining, washing, oven dry, obtain thering is the mesoporous of dendroid pore passage structureSiO2Nano particle, productive rate 65%, average grain diameter 50nm. Attached Fig. 1 and 2 shows, the mesoporous SiO2 nano particle that the method is syntheticSize homogeneous, specific area 1300m2/ g, pore volume 2.3ml/g, between the 3～20nm of aperture; Duct have significantly by inner toOuter divergent shape pore passage structure, i.e. the dendroid pore passage structure of doing of bibliographical information.
Embodiment 2
First 2.74g cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt (CTATos) is joined contain 144ml go fromSub-water, 0.15g triethanolamine (TEAH3) beaker in, 80 DEG C of constant temperature stir and become clarification to solution in 1 hour, then by 20.83gTetraethoxy esters of silicon acis (TEOS) joins rapidly in this beaker, stirs, after 30 minutes, 8.33gF127 is added to mixed solutionIn, 80 DEG C of constant temperature continue to stir 1 and a half hours, obtain stable colloidal suspension liquid, this mixture mole consist of SiO2:CTATos:TEAH3:F127:H2O=1:0.06:1:0.0095:80; By the mixture high speed centrifugation, washing, the oven dry that obtain,Arrive the mesoporous SiO2 nano particle of the dendroid pore passage structure of bulky grain size, productive rate 73%, average grain diameter 120nm; Specific surfaceLong-pending 1200m2/ g, pore volume 1.8ml/g, between the 3.1～20nm of aperture, accompanying drawing 3 and 4.
Embodiment 3
Except replacing the tetraethoxy esters of silicon acis (TEOS) in embodiment 1 with tetramethoxy esters of silicon acis (TMOS), other systemStandby condition is all identical with embodiment 1, obtains the mesoporous SiO of dendroid pore passage structure2Nano particle average grain diameter is 30nm.
Comparative example
First 2.74g cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt (CTATos) is joined contain 144ml go fromTriethanolamine (the TEAH of sub-water, 14.92g3) beaker in, 80 DEG C of constant temperature stir and become clarification to solution in 1 hour, then will20.83g tetraethoxy esters of silicon acis (TEOS) joins rapidly in this beaker, and 80 DEG C of constant temperature continue to stir 2 hours, static obtainingWhite precipitate, this mixture mole consist of SiO2:CTATos:TEAH3:H2O=1:0.06:1:80; By the mixing obtainingThe direct suction filtration of thing, washing, oven dry, obtain the mesoporous SiO containing dendroid pore passage structure2Nano particle, productive rate 93%, average grain diameter125nm。
In comparative example, reaction finish rear finally obtain for white precipitate, containing the mesoporous SiO2 of dendroid pore passage structureNano particle can obtain by the way of direct suction filtration; And add after triblock copolymer F127, obtain as stable colloidal stateSolution, the mesoporous SiO2 nano particle of dendroid pore passage structure only has the way acquisition by high speed centrifugation sedimentation.
Claims (4)
1. a preparation method for dendroid pore passage structure mesoporous spherical nano Sio 2 particle, is characterized in that the method bagDraw together following concrete steps:
A, by deionized water, organic molecule amine, cation template and cosurfactant F127 add successively reaction holdIn device, 80 DEG C of constant temperature are stirred to solution clarification, obtain surfactant solution;
B, silicon source is joined rapidly in step a solution, 80 DEG C of constant temperature stir 2 hours, transfer to reactor after being cooled to room temperatureMiddle crystallization or directly by centrifugal product, wash and be dried, obtain described dendroid pore passage structure mesoporous silica spheres shape nanometerParticle; Wherein:
The mol ratio of material is silicon source: cation template: organic molecule amine: cosurfactant F127: deionized water=1:0.03～0.06:0.001～8.0:0.0001～0.1:20～1000；
Described cation template is cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt, is called for short CTATos; CosurfactantF127 is the large molecule of a kind of three block neutral polymer, is abbreviated as F127; Silicon source is tetraalkyl esters of silicon acis;
Described organic molecule amine be tri methylol amino methane, ethamine, propylamine, butylamine, triethylamine, tripropyl amine (TPA), triethanolamine,Monoethanolamine or diethanol amine.
2. a preparation method for dendroid pore passage structure mesoporous spherical nano Sio 2 particle, is characterized in that the method bagDraw together following concrete steps:
A, deionized water, organic molecule amine, cation template and silicon source are added in reaction vessel successively to 80 DEG C of constant temperatureBe stirred to solution clarification;
B, cosurfactant F127 is joined rapidly in step a solution, 80 DEG C of constant temperature stir 2 hours, are cooled to after room temperatureTransfer in reactor crystallization or directly by centrifugal product, wash and be dried, obtain the mesoporous dioxy of described dendroid pore passage structureSiClx spherical nanoparticle; Wherein:
The mol ratio of material is silicon source: cation template: organic molecule amine: cosurfactant F127: deionized water=1:0.03～0.06:0.001～8.0:0.0001～0.1:20～1000；
Described cation template is cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt, is called for short CTATos; CosurfactantF127 is the large molecule of a kind of three block neutral polymer, is abbreviated as F127; Silicon source is tetraalkyl esters of silicon acis;
Described organic molecule amine be tri methylol amino methane, ethamine, propylamine, butylamine, triethylamine, tripropyl amine (TPA), triethanolamine,Monoethanolamine or diethanol amine.
3. method according to claim 1 and 2, it is characterized in that described tetraalkyl esters of silicon acis be tetramethoxy esters of silicon acis orTetraethoxy esters of silicon acis.
4. method according to claim 1 and 2, it is characterized in that by regulate amount that cosurfactant F127 adds andThe order that it adds before and after the silicon source, can realize the particle diameter of mesoporous silicon oxide of dendroid pore passage structure at 20～200nmBetween accurately regulation and control.
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| CN109399638A (en) * | 2018-12-10 | 2019-03-01 | 中国医科大学 | A kind of preparation method of dendroid silicon nanoparticle |
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